Ceramic Composite Materials

ABSTRACT

Composite ceramic materials are disclosed in which an interconnected network of ceramic material on a substrate contains pores with an accessible pore volume that is at least partially filled with a polymer, resin, and/or wax.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to PCT Application No. PCT/US2019/065978, filed on Dec. 12, 2019, and claims the benefit of U.S. Provisional Application No. 62/989,092, filed on Mar. 13, 2020, 62/989,150, filed on Mar. 13, 2020, 63/038,642, filed on Jun. 12, 2020, 63/038,693, filed on Jun. 12, 2020, and 63/039,965, filed on Jun. 16, 2020, all of which are incorporated herein by reference in their entireties.

FIELD OF THE INVENTION

The invention relates to ceramic composites, in particular composites of a porous ceramic material in which an interconnected network of ceramic contains an accessible pore volume that is at least partially filled with a polymer, resin, and/or wax.

BACKGROUND

Composite materials can provide synergistic benefits through the incorporation of properties from each of the materials that comprise the composite. Metal substrates, in particular aluminum substrates, can suffer from poor adhesion of added layers and can also suffer from corrosion in the event that the native oxide is compromised. Polymer, resin and wax materials are often used to provide protection to an underlying substrate or to modify how the substrate interacts with the environment. Direct application of these materials to smooth metal substrates can result in poor adhesion or aesthetic challenges such as drips, runs and spots, or other problems related to the amount of material applied. A material with better adherence, uniformity, and/or aesthetic properties would be desirable.

BRIEF SUMMARY OF THE INVENTION

Composite materials and compositions containing the composite materials are provided. Applications of use of the composite materials are also provided.

In one aspect, a composition is provided that includes: (i) a composite material that includes a polymer, wax, and/or resin impregnated into a porous ceramic material, wherein the porous ceramic material includes an interconnected network of pores with an accessible pore volume that is at least partially filled with the polymer, wax, and/or resin; and (ii) a substrate, wherein the composite material is in contact with the substrate. In some embodiments, at least a portion or substantially all of the composite material is in direct contact with the substrate. In some embodiments, at least about 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% of the ceramic material by mass is interconnected.

In some embodiments, the substrate and the ceramic material each include a primary metal, and the primary metal in the ceramic material is different than the primary metal in the substrate. In other embodiments, the substrate and the ceramic material each include a primary metal, and the primary metal in the ceramic material is the same as the primary metal in the substrate.

In some embodiments, the composite material has a thickness of about 1 micrometer to about 100 micrometers.

The ceramic material may include a rare earth element, a transition metal element, an alkaline earth metal element, or aluminum. The ceramic material may include an oxide, a hydroxide, and/or a layered double hydroxide. In some embodiments, the oxide, hydroxide, and/or layered double hydroxide includes iron, aluminum, magnesium, cerium, zinc, manganese, titanium, chromium, nickel, cobalt, copper, silver, tantalum, tungsten, silicon, phosphorus, tin, vanadium, zirconium, calcium, barium, or europium.

The substrate may include an aluminum alloy, a steel alloy, a nickel alloy, a titanium alloy, a polymer, a polysaccharide, or a cellulosic material (e.g., wood, cotton), or glass.

In various embodiments, the polymer, wax, and/or resin may impart one or more functional characteristic to the composite material, selected from: enhanced hardness, elasticity, viscoelasticity, adhesion, thermal properties, aesthetic appearance, liquid repellency, sound dampening, light scattering, and corrosion resistance, in comparison to an identical ceramic material that does not include the polymer, wax, and/or resin, on an identical substrate.

In one embodiment, the ceramic material is a binderless ceramic material. In some embodiments, the polymer, wax, and/or resin includes a natural polymer, such as a polymer derived from tung oil, linseed oil, walnut oil, natural rubber, cellulose, or chitin. In some embodiments, the polymer, wax, and/or resin includes a synthetic polymer, such as a polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, a polyester, such as polyethylene terephthalate, a polyacrylate, such as poly(methyl methacrylate), polyvinyl acetate, polyether, polychloroprene, poly(vinyl chloride), polyurethane, polyamide, polyimide, silicone, poly(dimethyl siloxane), or polyepoxide polymer. In some embodiments, the polymer, wax, and/or resin includes a silane, a silicate (e.g., potassium silicate, sodium silicate), a siliconate (e.g., potassium methyl siliconate, sodium methyl siliconate), an organotriethoxysilane, or an organotrimethoxysilane, a polysilazane (e.g., Durazane 1500, Durazane 1800, or Durazane 2200). In some embodiments, the polymer, wax, and/or resin includes a petroleum wax (e.g., paraffin wax), an animal produced wax (e.g., beeswax, lanolin, shellac), a plant derived wax (e.g., palm wax, carnauba wax, soy wax), or a mineral derived wax (e.g., ceresin, montan).

In some embodiments, the polymer, wax, and/or resin includes one or more additional additive, such as, but not limited to, a lubricant, a plasticizer, a flame retardant, a dye, a UV-stabilizer, a free radical scavenger, or a cross-linking agent. For example, the additive may impart one or more structural or functional property to the composite material, such as, but not limited to, viscosity, flexibility, flammability, color, UV stability, chemical reactivity, and/or degree of cross linking.

In some embodiments, at least about 1%, e.g., about 1% to about 99%, of the pore volume of the ceramic material is filled with the polymer, wax, and/or resin, as determined by mercury porosimetry testing.

In some embodiments, the thickness of the polymer, resin, and/or wax is less than about 1.5 times the thickness of the ceramic material.

In some embodiments, the ceramic material interacts with the polymer, wax, and/or resin material, thereby altering one or more property of the polymer, wax, and/or resin. In one example, the interaction may increase rate and/or degree of cross-linking, e.g., cross-linking of carbon chains, of said polymer, wax, and/or resin, in comparison to the rate and/or degree of cross-linking when the polymer, wax and/or resin is applied directly to an identical substrate that does not comprise the ceramic material. In another example, the interaction may increase degree of crystallinity of the polymer, wax, and/or resin material, in comparison to degree of crystallinity when the polymer, wax, and/or resin material applied directly to an identical substrate that does not comprise the ceramic material. In another example, the interaction may decrease rate of UV degradation of the polymer, wax, and/or resin material, in comparison to rate of UV degradation of the polymer, wax, and/or resin material applied directly to an identical substrate that does not comprise the ceramic material. In one nonlimiting example, zinc oxide in the ceramic material may act as a UV absorber.

In some embodiments, the ceramic material includes magnesium, manganese, a zinc oxide, or an aluminum oxide or hydroxide, and the polymer, wax, and/or resin includes a drying oil such as tung oil or paraffin.

In some embodiments, the ceramic material includes magnesium, manganese, a zinc oxide, or an aluminum oxide or hydroxide, and the polymer, wax, and/or resin reacts chemically with the ceramic material to modify one or more property of the polymer, wax, and/or resin. For example, the chemical reaction to modify the property(ies) of the polymer, wax, and/or resin may include crosslinking, hardening, and/or polymerization of the polymer, wax, and/or resin.

In some embodiments, a composite material as described herein is used to provide one or more functional property to the substrate, such as, but not limited to: corrosion protection for the substrate; durability modifier for adhesion and/or fouling surfaces; adhesion promoting or retarding configuration; tactile modified surface; liquid repellency application; optical property modification; mechanical modification such as hardness, elasticity and viscoelasticity; surface and scratch self-healing and repair purposes; separations applications; electrical property modification or electrical property applications; ice, condensate and frost mitigation and/or modification; or aesthetic properties, wherein the functional property is improved or of greater magnitude than an identical porous ceramic material without the polymer, resin, and/or wax on an identical substrate, or improved or of greater magnitude than the polymer, resin, and/or wax applied directly to an identical substrate.

In some embodiments, the composite material comprises a critical pigment or ceramic volume concentration that exceeds that of a paint. In some embodiments, the volume concentration of the pigment or ceramic is greater than any of about 40%, about 50%, about 60%, about 70%, about 80%, or about 90% of the total volume of the composite material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an X-ray diffraction spectrum of the ceramic material described in Example 1.

FIGS. 2A-2C show a comparison of porous ceramic coated, composite material coated, and uncoated aluminum plates, as described in Example 11. FIG. 2A: porous ceramic surface; FIG. 2B: porous ceramic surface partially filled with RTV silicone; FIG. 2C; aluminum plate top coated with RTV silicon

FIGS. 3A-3C show a comparison of porous ceramic coated, composite material coated, and uncoated aluminum plates as described in Example 12. FIG. 3A: porous ceramic surface; FIG. 3B: porous ceramic surface top coated with PDMS; FIG. 3C: aluminum plate top coated with PDMS

FIGS. 4A-4C show a comparison of porous ceramic coated, composite material coated, and uncoated aluminum plates, subjected to corrosive salt spray, as described in Example 16. FIG. 4A: porous ceramic surface; FIG. 4B: aluminum plate coated with polyurethane surface treatment; 4C: porous ceramic filled with polyurethane top coat

FIGS. 5A-5C show a comparison of porous ceramic coated, composite material coated, and uncoated aluminum plates, subjected to crosshatch adhesion testing, as described in Example 17. FIG. 5A: porous ceramic surface; FIG. 5B: aluminum plate coated with polyacrylic sealant; FIG. 5C: porous ceramic filled with polyacrylic sealant

FIGS. 6A-6B shows a comparison of a sagging, a visual coating defect observed on the aluminum plate when coated with acrylic sealant. FIG. 6A: Aluminum plate coated with acrylic sealant showed sagging; FIG. 6B: porous ceramic surface coated with acrylic sealant has no sagging defect.

FIGS. 7A-7C shows a comparison of a self-leveling effect progression with time on a porous ceramic substrates compared to a bare aluminum substrate. An epoxy-based resin achieved lower contact angle in 10 min on a zinc oxide-based (FIG. 7B) and manganese oxide-based (FIG. 7C) porous ceramic substrates compared to (FIG. 7A) a bare aluminum panel.

FIG. 8 shows a comparison of a self leveling effect observed on porous ceramic substrates. An epoxy-based resin exhibited a lower contact angle, and hence more self-levelling on zinc- and manganese-based coated porous ceramic substrates compared to the bare aluminum substrate.

FIG. 9 shows the wicking behavior of paraffin wax on aluminum plates coated with mixed zinc/aluminum oxide and mixed manganese/aluminum oxide ceramics, as described in Example 22.

FIG. 10 shows the wicking behavior of paraffin wax progression with time on Zn and Mn based porous ceramic coated substrates compared to bare aluminum. More wicking, and hence improved (more uniform) coverage is achieved in 5 min on porous ceramic coated substrates compared to the bare aluminum panel.

DETAILED DESCRIPTION

Ceramic composite materials are provided herein. The composites include a porous ceramic material that contains an interconnected ceramic network. At least a portion of the accessible pore volume is at least partially filled with a polymer, resin, and/or wax. The ceramic composite is deposited on a substrate. The composite materials described herein provide beneficial properties, such as good adhesion to a substrate, and can be used to apply uniform external coatings to a substrate, such as a metal substrate, and/or to impart desirable aesthetic properties, such as, but not limited to, minimization or elimination of drips, runs and spots that are often associate with polymers, resins, and/or waxes applied directly to a substrate as described herein.

Definitions

Numeric ranges provided herein are inclusive of the numbers defining the range.

“A,” “an” and “the” include plural references unless the context clearly dictates otherwise.

The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified unless clearly indicated to the contrary. Thus, as a non-limiting example, a reference to “A and/or B,” when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.”

“Binder” or “binding agent” is any material or substance that holds or draws other materials together to form a cohesive whole mechanically, chemically, by adhesion or cohesion.

“Binderless” refers to absence of a binder that may be exogenously added to a primary material to improve structural integrity, particularly with regard to an organic binder or resin (e.g., polymers, glues, adhesives, asphalt) or inorganic binder (e.g., lime, cement glass, gypsum, etc.).

“Capillary climb” refers to a surface tension driven flow of liquid up a sample (the capillary climb is parallel to, and opposite to, the direction of the force (vector) due to gravity) upon contact with a free surface of liquid as a result of the porous substrate.

A “cellulosic” material refers to a material that is constructed of or that contains cellulose or derivatives of cellulose, e.g., ethers or esters of cellulose.

A “ceramic” or “ceramic material” refers to a solid material that includes an inorganic compound of a metal or a metalloid, and a non-metal, with ionic or covalent bonds. A “non-metal” may include oxygen (oxide ceramic), or carbon (carbide) or nitrogen (nitride) (non-oxide ceramics). A “metal” may include a non-hydrogen element of Group 1 of the periodic table, an element of Groups 2-12 of the periodic table, or an element from the p-block (Groups 12-17 of the periodic table), e.g., Al, Ga, In, TI, Sn, Pb, Bi, or combinations thereof. A “metalloid” may include B, Si, Ge, As, Sb, Se, Te, or Po, or combinations thereof.

“Contact angle” refers to the angle measured through a liquid between a surface and the liquid-vapor interface at the contacting surface.

“Contiguous” or “contiguity” refers to pores and structures that contain walls and features in direct contact with one another or that share a common wall across a region or dimension large relative to an individual pore or structure.

A “conversion coating” refers to a surface layer in which reactants are chemically reacted with the surface to be treated, which converts the substrate into a different compound. This process is typically not additive or a deposition, but may result in a small mass change.

“First quartile pore diameter” refers to the value of the pore diameter at which the cumulative pore surface area determined in the direction of increasing pore size is equivalent to 25% of the total cumulative pore surface area as determined by BJH gas adsorption/desorption measurements.

A “functional material layer” refers to a layer of material which may serve as the uppermost surface layer interacting with the surrounding environment or may serve as an interfacial layer for subsequent materials (intermediate layer between two other layers of material). A functional material layer imparts one or more desirable functional properties to the underlying substrate and/or the material on which it is deposited.

A “gradient” refers herein to a quantitative increase or decrease in one or more physical or chemical property of a material observed by passing spatially from one point to another point along a substrate surface on which the material is situated or immobilized, and varying in an x, y, or z direction in Cartesian coordinates on or through the material. Nonlimiting examples of gradient properties include thickness, density, hardness, ductility, pore size, pore size distribution, pore filling fraction, or chemical or physical composition, including but not limited to, oxidation state, metal concentration, or crosslinking density, for example, resulting in variation in isoelectric point, electrical conductivity, thermal conductivity, capacitance, etc.

“Hydrophilic” refers to a surface that has a high affinity for water. Contact angles can be very low (e.g. less than 30 degrees as measured from the surface through the liquid water in the presence of air) and/or immeasurable.

An “impregnated” polymer, resin and/or wax refers to a polymer, resin, and/or wax that is dispersed within the pores of a porous ceramic material as described herein.

“Interconnected ceramic network” or “interconnected network of ceramic” refers to a network or matrix of ceramic material, wherein ceramic material in the network is in physical contact with (connected to) other ceramic material in the network. This is in contrast to a suspension comprising ceramic particles, such as a paint, in which individual ceramic particles are suspended in a medium such as a binder, resin, oil, or wax and in which the ceramic particles are not in fixed contact with one another. The interconnected ceramic network described herein is a continuous ceramic phase over a macroscopic area or volume, and may contain pores (open spaces) within the ceramic network with an accessible pore volume, which may be filled, or partially filled, with another material.

“Layered double hydroxide” refers to a class of ionic solids characterized by a layered structure with the generic sequence [AcB Z AcB]_(n), where c represents layers of metal cations, A and B are layers of hydroxide anions, and Z are layers of other anions and/or neutral molecules (such as water). Layered double hydroxides are also described in PCT Application No. PCT/US2017/052120, which is incorporated by reference herein in its entirety.

A “macro void” refers to a geometric space within solid that has a characteristic dimension substantially larger than the characteristic dimension of an individual pore or feature (e.g., thickness), for example, at least about 5× to about 10× or about 10× to about 100× greater than the characteristic dimension.

“Mean” refers to the arithmetic mean or average.

“Mean pore diameter” is calculated using total surface area and total volume measurements from the Barrett-Joyner-Halenda (BJH) adsorption/desorption method as 4 times the total pore volume divided by the total surface area (4V/A), assuming a cylindrical pore.

“Multimodal” refers to a distribution which contains more than one different mode that appears as more than one distinct peak.

“Permeability” in fluid mechanics is a measure of the ability of a porous material to allow fluids to pass through it. The permeability of a medium is related to the porosity, but also to the shapes of the pores in the medium and their level of connectedness.

“Pore size distribution” refers to the relative abundance of each pore diameter or range or pore diameters as determined by mercury intrusion porosimetry (MIP) and Washburn's equation.

“Porosity” is a measure of the void (i.e., “empty”) spaces in a material, and is a fraction of the volume of voids, i.e., macro voids. over the total volume, between 0 and 1, or as a percentage between 0% and 100%. Porosities disclosed herein were measured by mercury intrusion porosimetry.

“Porous” refers to spaces, holes, or voids within a solid material.

A “resin” refers herein to a solid or high viscosity substance that comprises a mixture of compounds of plant or synthetic origin that is or that can be partially or completely converted into polymers.

“Superhydrophobic” refers to a surface that is extremely difficult to wet. The contact angle of a water droplet on a superhydrophobic material here a superhydrophobic surface refers to a sessile drop contact angles >150°. Highly hydrophobic contact angles are >120°. Contact angles noted here are angles formed between the surface through the liquid.

“Surface area per square meter of projected substrate area” refers to the actual measured surface area, usually measured in square meters, divided to the surface area of the substrate if it were atomically smooth (no surface roughness), also typically in square meters.

“Synergy” or “synergistic” refers to the interaction or cooperation between two or more substances, materials, or agents to produce a combined effect that is greater (positive synergy) or lesser (negative synergy) than the sum of theft separate, individual effects.

“Thickness” refers to the length between the surface of the substrate and the top of the surface modification (e.g., ceramic) material.

“Third quartile pore diameter” refers to the value of the pore diameter at which the cumulative pore surface area determined in the direction of increasing pore size is equivalent to 75% of the total cumulative pore surface area as determined by BJH gas adsorption/desorption measurements.

“Tortuosity” refers to the fraction of the shortest pathway through a porous structure Δl and the Euclidean distance between the starting and end point of that pathway Δx.

“Tunable” refers to the ability of a function, characteristic, or quality of a material to be changed or modified.

A “wax” refers herein to naturally or synthetically produced organic compounds that include hydrocarbons that are typically lipophilic, malleable solids at moderate temperatures and lower viscosity liquids at elevated temperatures. Waxes typically include long aliphatic alkyl chains, and can also contain a variety of functional groups including fatty acids, lipids, alkanes, primary and secondary alcohols, ketones, aldehydes, and fatty acid esters. Synthetic waxes often include a homologous series of long-chain aliphatic hydrocarbons (alkanes or paraffins) that lack functional groups.

Ceramic Composites

Ceramic composite materials are provided herein. The composites include a polymer, wax, and/or resin impregnated within the pores of an interconnected ceramic network. The polymer, wax, and/or resin at least partially fills at least a portion of the accessible pore volume of the ceramic network. The ceramic network includes a collection of pores within the ceramic base material network. The pores may be interconnected (typically open cell), independent (typically closed cell) or a combination of interconnected and independent (mixed cell). The pores may be fluidically separated by ceramic walls, but linked or connected by the ceramic therebetween. For example, any of at least about 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99%, or 99.5% of the ceramic by mass is interconnected (ceramic material between pores in contact with other ceramic material), i.e., in contrast to unconnected ceramic particles surrounded by another material such as a polymer, resin, and/or wax.

The ceramic composite materials described herein differ from a paint in that pigment or ceramic particles are in suspension in a paint, and once a paint is applied to a surface, the pigment or ceramic particles are typically surrounded by and are primarily in physical contact with the resin, polymer, wax, or oil relative to other ceramic particles or pigment within the paint. The pigment or ceramic particles in paint are in suspension in the paint formulation and are not in fixed contact with one another, in contrast to the ceramic composition materials described herein, which contain an interconnected ceramic network. Paint is typically formulated below the critical pigment volume concentration to ensure the binder can coat all pigment, to prevent interconnected pigment or ceramic networks from forming, and to prevent voids. The ceramic composite materials described herein include ceramic material that is interconnected without resin, polymer, wax, or oil separating the ceramic or pigment from other ceramic particles or pigment. In some embodiments, the majority of the interconnected ceramic network within the composite material is interconnected into a single network. In other embodiments, the interconnected ceramic network is applied to discrete portions of the substrate. In some embodiments the continuity of the interconnected ceramic network may be interrupted by cracks within the interconnected ceramic network, forming islands of interconnected ceramic network. In some embodiments the islands of interconnected ceramic network within the composite material have an arithmetic mean or median area, as projected on the nominal average plane of the associated substrate, that is about 10 square micrometers to about 1 square centimeter, about 1000 square micrometers to about 10,000 square millimeters, about 5000 square micrometers to about 50,000 square millimeters, about 20,000 square millimeters to about 100,000 square millimeters, about 250,000 square millimeters to about 1 square centimeter, or larger than any of about 10 square micrometers, about 50 square micrometers, about 100 square micrometers, about 200 square micrometers, about 500 square micrometers, about 1000 square micrometers, about 2000 square micrometers, about 5000 square micrometers, about 10,000 square millimeters, about 20,000 square millimeters, about 50,000 square millimeters, about 100,000 square millimeters, about 500,000 square millimeters, or about 1 square centimeter. In some embodiments, substantially all of the ceramic within the composite material is interconnected.

The ceramic material may include a rare earth element, a transition metal, an alkaline earth metal, and/or aluminum. The ceramic material may be in the form of a metal oxide, a metal hydroxide, or a layered double hydroxide, or a combination thereof. For example, ceramic may include, but is not limited to, one or more element selected from iron, aluminum, magnesium, cerium, zinc, manganese, titanium, chromium, nickel, cobalt, copper, silver, tantalum, tungsten, silicon, phosphorous, tin, and europium.

The ceramic material may be electrically conducting, insulating, or semiconducting. In some embodiments the ceramic material is more electrically resistive than the substrate. In other embodiments the ceramic material is more electrically conductive than the substrate. In some embodiments the ceramic material is a semiconductor with a band gap between about 0.1 eV and about 4 eV. In some embodiments the ceramic material photo-active, piezo-active, or capable of generating electricity upon application of a pressure or heat gradient. In some embodiments the ceramic material is a thermal insulator. In other embodiments the ceramic material is a thermal conductor.

The interconnected ceramic network material is deposited onto a substrate. In some embodiments, the interconnected ceramic network material is immobilized on the substrate. In some embodiments, the interconnected ceramic network material is a binderless porous ceramic material on the substrate. In some embodiments, the interconnected ceramic network material may be in direct contact with the substrate. In other embodiments, the interconnected ceramic network material may be in indirect contact with the substrate, for example, in contact with a surface modification or treatment on the substrate surface. The substrate may include a metal or metal alloy (such as, but not limited to, aluminum, steel, titanium, or an alloy thereof), a polymer, a polysaccharide, a cellulosic material, wood, cotton, or glass. In some embodiments, the substrate includes one or more metal, and the primary metal in the substrate is different than the primary metal in the ceramic material.

The thickness of the composite material on the substrate may be about 1 micrometer to about 100 micrometers. For example, the composite material may be about 1 μm to about 10 μm about 5 μm to about 25 μm, about 10 μm to about 50 μm, about 25 μm to about 75 μm, about 50 μm to about 100 μm, about 1 μm to about 25 μm, about 10 μm to about 100 μm, or any of at least about 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 90 μm, 95 μm, or 100 μm in thickness.

In some embodiments, about 1% to about 99% of the accessible pore volume of the ceramic material is filled with the polymer, resin, and/or wax, for example, as determined by mercury porosimetry testing. For example, about 1% to about 5%, about 5% to about 20%, about 10% to about 30%, about 20% to about 40%, about 30% to about 50%, about 40% to about 60%, about 50% to about 70%, about 60% to about 80%, about 70% to about 90%, about 80% to about 99%, about 1% to about 20%, about 10% to about 50%, about 25% to about 75%, about 50% to about 99%, about 10% to about 90%, about 1% to about 99.9%, or any of at least about 1%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% to about 99% of the pore volume is filled with the polymer, resin, and/or wax.

In one example, the polymer, resin, and/or wax fills a portion of the accessible ceramic pore volume, but also is thicker than the thickness of the porous ceramic structure (interconnected ceramic network) (e.g., protrudes from the pores of the porous ceramic structure). In another example, the polymer, resin, and/or wax fills a portion of the accessible pore volume, but is not thicker than the porous ceramic structure (e.g., is contained within the pores of the porous ceramic structure (interconnected ceramic network)).

In some embodiments, the polymer, resin, and/or wax is in the form of a layer that is less than about 1.5 times the thickness of the ceramic material. In some embodiments, the polymer, resin, and/or wax is in the form of a layer that is up to any of about 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 times the thickness of the ceramic material.

Nonlimiting examples of natural polymers in composite materials as described herein include: tung oil, linseed oil, walnut oil, natural rubber, cellulose, and chitin. Nonlimiting examples of synthetic polymers in composite materials as described herein include: polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyethylene terephthalate, poly(methyl methacrylate), polyvinyl acetate, polychloroprene, poly(vinyl chloride), polyurethane, polyamide, polyimide, poly(dimethyl siloxane), polysilazane, and polyepoxide, and co-polymers thereof.

Nonlimiting examples of polymers or resins in composite materials as described herein include: silanes, silicates (such as sodium silicate or potassium silicate), siliconates (such as sodium methyl siliconate or potassium methyl siliconate), a polysilazane, organotriethoxysilanes, and oragnotrimethoxysilanes, and shellac.

Nonlimiting examples of waxes in composite materials as described herein include: petroleum, animal produced, plant derived, and mineral derived waxes, such as, for example, paraffin wax, beeswax, lanolin, palm wax, carnauba wax, soy wax, ceresin, and montan.

The polymer, resin, and/or wax may include one or more additive that imparts a functional or chemical/physical property, such as, but not limited to, a lubricant (e.g., imparting viscosity), a plasticizer (e.g., imparting flexibility), a flame retardant (imparting flammability resistance), a dye or pigment (imparting color), an ultraviolet (UV) stabilizer (imparting UV stability), a free radical scavenger (e.g., imparting resistance to chemical reactivity), or a cross-linking agent (imparting degree of cross-linking).

In some embodiments of the composite materials described herein, the polymer, resin, and/or wax may chemically or physically interact with the ceramic material, providing a desirable functional or structural characteristic. For example, the interaction may increase the rate and/or degree of cross-linking of the polymer, resin, and/or wax, in comparison to the cross-linking of the polymer, resin, and/or wax when applied or deposited directly onto an identical substrate that does not include the ceramic material. In another example, the interaction may increase the degree of crystallinity of the polymer, resin, and/or wax, in comparison to the degree of crystallinity of the polymer, wax, and/or resin when applied or deposited directly onto an identical substrate that does not include the ceramic material. In another example, the interaction may decrease the rate of UV degradation of the polymer, resin, and/or wax, in comparison to UV degradation of the polymer, resin, and/or wax when applied or deposited directly onto an identical substrate that does not include the ceramic material. In some embodiments, the ceramic material and the polymer, wax, and/or resin interact synergistically, providing one or more functional property that is improved or enhanced versus either material alone deposited on an identical substrate.

In some embodiments, the porous or structured ceramic material is used to enhance the transport or wicking of the polymer, wax, or resin to aid in its flow around edges and/or to make a more uniform layer in thickness. In some embodiments, the structured ceramic layer allows for the uniform spraying of a polymer, wax, or resin on a substrate with complex geometries or tight spacings, such as in a heat exchanger. In some embodiments, the composite material provides equivalent performance to a paint or polymer, wax, or resin coated substrate without the structured ceramic layer, while using less material. In some embodiments, the composite material reduces or eliminates defects such as, but not limited to, alligatoring, bleeding, blistering, blooming, blushing, bridging, bubbling, chalking, checking cissing, cobwebbing, cratering, crazing, crows-footing, flaking, mud cracking, orange peeling, pinholes, ripples, running, sagging, solvent lifting, and/or stress cracking.

In some embodiments, multiple polymers, waxes, and/or resins are used to create the composite material. In some embodiments a first polymer layer is used to partially fill the pores of the structured ceramic material layer. In some embodiments, a second polymer layer is used to further fill the pores of the ceramic material. In some embodiments a sanding step between the layers is not needed or is reduced in magnitude relative to depositing multiple polymer, resin, and/or wax layers on a substrate without the interconnected structured ceramic layer.

Applications of Use

The composite materials described herein may be used for a variety of applications including corrosion protection for substrates, durability modifiers for adhesion and fouling surfaces, adhesion promoting or retarding configurations, tactile modified surfaces, liquid repellency, modification of microbial, viral and fungal properties, optical property modification, mechanical modification such as hardness, elasticity and viscoelasticity, surface and scratch self-healing and repair, separations, electrical property modification, ice, condensate and frost mitigation and modification, or aesthetic properties. The composite material may provide an improvement in any one or any combination of the above functional properties, in comparison to an identical porous ceramic material that does not include the polymer, wax, and/or resin on an identical substrate, or in comparison to an identical polymer, wax, and/or resin applied directly to an identical substrate.

Structured Ceramic Materials

A continuous or discrete coating or surface modification material as described herein may be a structured ceramic, for example, a binderless (e.g., surface immobilized) ceramic, such as a binderless ceramic with a crystallinity greater than about 20%. The structured ceramic is porous, i.e., the interconnected ceramic network material contains voids or pores. Nonlimiting examples of ceramic materials are provided in PCT/US19/65978, which is incorporated herein by reference in its entirety.

The ceramic material may include a metal oxide and/or hydroxide ceramic, for example, a single metal or mixed metal oxide and/or hydroxide ceramic. In some embodiments, the ceramic material includes a metal hydroxide and/or hydroxide ceramic, for example, a single metal or mixed metal oxide and/or hydroxide ceramic. In some embodiments, the ceramic material includes a metal oxide and a metal hydroxide ceramic, wherein the metal oxide and the metal hydroxide include the same or different single metal or mixed metal. In some embodiments, the ceramic material includes a metal oxide and/or a metal hydroxide ceramic, wherein the substrate is hydrated by water or other compounds resulting in a change of surface energy and potentially the ratio of metal oxide to metal hydroxide composition of the ceramic. In some embodiments, the ceramic material includes a metal hydroxide, wherein at least a portion of the metal hydroxide is in the form of a layered double hydroxide, e.g., at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the metal hydroxide is layered double hydroxide.

In some embodiments, a “metal oxide” or “metal hydroxide” may be in the form of a hydrate of a metal oxide or metal hydroxide, respectively, or a portion of the metal oxide or metal hydroxide may be in the form of a hydrate of a metal oxide or metal hydroxide, respectively.

A mixed metal oxide or mixed metal hydroxide may include, for example, oxides or hydroxides, respectively, of more than one metal, such as, but not limited to, iron, cobalt, nickel, copper, manganese, chromium, titanium, vanadium, zirconium, molybdenum, tantalum, zinc, lead, tin, tungsten, cerium, praseodymium, samarium, gadolinium, lanthanum, magnesium, aluminum, or calcium.

In some embodiments, the ceramic material is a binderless ceramic material, i.e., deposited onto a substrate without a binder. In some embodiments, the ceramic materials immobilized on the substrate.

In some embodiments, the interconnected ceramic network material has an open cell porous structure, for example, characterized by one or more of: ability to effect capillary rise of a liquid having a low surface tension (e.g., less than about 25 mN/m, such as isopropanol) at greater than about 5 mm up a surface against gravity in a closed container in 1 hour; surface area of about 0.1 m²/g to about 10,000 m²/g; mean pore size of about 10 nm to about 1000 nm or about 1 nm to about 1000 nm; pore volume as measured by mercury (Hg) intrusion porosimetry of about 0 to about 1 cc/g; and tortuosity of about 1 to about 1000 as defined by the length of a fluid path to the shortest distance, the “arc-chord ratio”; and/or permeability of about 1 to about 10,000 millidarcy.

In some embodiments, the interconnected ceramic network has a porosity of about 5% to about 95%. In some embodiments, the porosity may be any of at least about or greater than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%. In some embodiments, the porosity is about 10% to about 90%, about 30% to about 90%, about 40% to about 80%, or about 50% to about 70%.

In some embodiments, the interconnected ceramic network material has a permeability of about 1 to 10,000 millidarcy. In some embodiments, the permeability may be any of at least about 1, 10, 100, 500, 1000, 5000, or 10,000 millidarcy. In some embodiments, the permeability is about 1 to about 100, about 50 to about 250, about 100 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 2000, about 1000 to about 2500, about 2000 to about 5000, about 3000 to about 7500, about 5000 to about 10,000, about 1 to about 1000, about 1000 to about 5000, or about 5000 to about 10,000 millidarcy.

In some embodiments, the interconnected ceramic network material includes a void volume of about 100 mm³/g to about 7500 mm³/g, as determined by mercury intrusion porosimetry. In some embodiments, the void volume is any of at least about 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, or 7500 mm³/g. In some embodiments, the void volume is any of about 100 to about 500, about 200 to about 1000, about 400 to about 800, about 500 to about 1000, about 800 to about 1500, about 1000 to about 2000, about 1500 to about 3000, about 2000 to about 5000, about 3000 to about 7500, about 250 to about 5000, about 350 to about 4000, about 400 to about 3000, about 250 to about 1000, about 250 to about 2500, about 2500 to about 5000, or about 500 to about 4000 mm³/g.

An interconnected ceramic network material as disclosed herein may be characterized by its interaction with liquid materials. As previously noted, the ceramic material may be characterized the ability to effect capillary rise of a liquid having a low surface tension (e.g., less than about 25 mN/m, such as isopropanol) at greater than about 5 mm up a surface against gravity in a closed container in 1 hour. Other solvents with surface tension less than about 25 mN/m at 20° C. of may be used including, but not limited to, Perfluorohexane, Perfluoroheptane, Perfluorooctane, n-Hexane (HEX), Polydimethyl siloxane (Baysilone M5), tert-Butylchloride, n-Heptane, n-Octane (OCT), Isobutylchloride, Ethanol, Methanol, Isopropanol, 1-Chlorobutane, Isoamylchloride, Propanol, n-Decane (DEC), Ethylbromide, Methyl ethyl ketone (MEK), n-Undecane, Cyclohexane. Other solvents with surface tension at 20° C. of >25 mN/m may be used including: Acetone (2-Propanone), n-Dodecane (DDEC), Isovaleronitrile, Tetrahydrofuran (THF), Dichloromethane, n-Tetradecane (TDEC), sym-Tetrachloromethane, n-Hexadecane (HDEC), Chloroform, 1-Octanol, Butyronitrile, p-Cymene, Isopropylbenzene, Toluene, Dipropylene glycol monomethylether, 1-Decanol, Ethylene glycol monoethyl ether (Ethyl Cellosolve), 1,3,5-Trimethylbenzene (Mesitylene), Benzene, m-Xylene, n-Propylbenzene, Ethylbenzene, n-Butylbenzene, 1-nitro propane, o-Xylene, Dodecyl benzene, Fumaric acid diethylester, Decalin, Nitroethane, Carbon disulfide, Cyclopentanol, 1,4-Dioxane, 1,2-Dichloro ethane, Chloro benzene, Dipropylene glycol, Cyclohexanol, Hexachlorobutadiene, Bromobenzene, Pyrrol (PY), N,N-dimethyl acetamide (DMA), Nitromethane, Phthalic acid diethylester, N,N-dimethyl formamide (DMF), Pyridine, Methyl naphthalene, Benzylalcohol, Anthranilic acid ethylester, Iodobenzene, N-methyl-2-pyrrolidone, Tricresylphosphate (TCP), m-Nitrotoluene, Bromoform, o-Nitrotoluene, Phenylisothiocyanate, a-Chloronaphthalene, Furfural (2-Furaldehyde), Quinoline, 1,5-Pentanediol, Aniline (AN), Polyethylene glycol 200 (PEG), Anthranilic acid methylester, Nitrobenzene, a-Bromonaphthalene (BN), Diethylene glycol (DEG), 1,2,3-Tribromo propane, Benzylbenzoate (BNBZ), 1,3-Diiodopropane, 3-Pyridylcarbinol (PYC), Ethylene glycol (EG), 2-Aminoethanol, sym-Tetrabromoethane, Diiodomethane (DI), Thiodiglycol (2,2′-Thiobisethanol) (TDG), Formamide (FA), Glycerol (GLY), Water (WA), and Mercury

The interconnected ceramic network material may possess the ability to effect capillary rise of water, at various temperatures. These materials may have the ability to separate miscible materials and binary azeotropes, such as ethanol-water, ethyl acetate-ethanol, or butanol-water, to break ternary azeotropes, or to remove amyl alcohol from mixtures including ethanol and water.

The pores of the interconnected ceramic network material may include open cells filled with one or more gas, may include partially filled cells (e.g., partially filled with one or more solid material(s)), or may include completely or substantially filled cells (e.g., completely or substantially filled with one or more liquid and/or solid material(s)). In some embodiments, the pores are partially, substantially, or completely filled with a gas, liquid, or solid substance, or combinations thereof.

In some embodiments, the pores are partially filled with a first material and then partially or completely filled with a second material. In one nonlimiting embodiment, the first material is a resin and the second material is a wax. In another nonlimiting embodiment, the first material is a resin and the second material is a sealant, protective top coat, protective finish or paint. In some embodiments, the second material is added as a layer of material over partially filled pores. In some embodiments, the first material is a gas, solid, or liquid, or combination of gas, liquid, and/or solid substance(s). In some embodiments, the second material is a gas, solid, and/or liquid substance(s), or the environment (e.g., air). Examples include, and functions thereby imparted include changes in the porosity, wicking, repellency and/or wetting behavior; changes in the composite (comprising the porous material and second material) to modify electrical/dielectric properties, to modify mechanical properties such as abrasion resistance, hardness, toughness, tactile feel, elastic modulus, yield strength, yield stress, Young's modulus, surface (compressive or tensile) stress, and/or elasticity; changes in thermal properties such as thermal diffusivity, conductivity, thermal expansion coefficient, thermal interface stress, and/or thermal anisotropy; modification of optical properties such as emissivity, color, reflectivity, and/or absorption coefficients; modification of chemical properties such as corrosion, catalysis, reactivity, inertness, compatibility, fouling resistance, ion pump blocking, microbial resistance, and/or microbial compatibility; and/or as a substrate for biocatalysis.

In some embodiments, the first material interacts with the second material in a positive or negative synergistic manner to alter one or more functional characteristic of the ceramic material, such as, but not limited to, wettability, hardness, elasticity, a mechanical, electrical, piezoelectric, optical, adhesion, or thermal property, microbial affinity or resistance, alteration of biofilm growth, catalytic activity, permeability, aesthetic appearance, liquid repellency, and/or corrosion resistance.

In some embodiments, the composite material described herein has a ratio of ceramic or pigment to resin that exceeds the critical pigment volume concentration of a paint. In some embodiments the ceramic or pigment concentration is greater than about 40%, about 50%, about 60%, about 70%, about 80%, or about 90% of the total volume of the composite material.

Polymers, resins, and/or wax materials, as described herein, may also be deposited into the pores, filling the pores partially, or substantially completely. Ceramic materials may include, for example, one or more oxide of zinc, aluminum, manganese, magnesium, cerium, gadolinium, and cobalt. In addition, ceramic materials may include any solid material which can be added to the surface modification material, including an inorganic compound of metal, non-metal, or metalloid atoms primarily held in ionic and covalent bonds, such as, for example, clays, silicas, and glasses. Polymers may include, for example, natural polymeric materials such as hemp, shellac, amber, wool, silk, natural rubber, cellulose, and other natural fibers, sugars, hemi- and holo-celluloses, polysaccharides, and biologically derived materials such as extracellular proteins, DNA, chitin. Synthetic polymers include, for example, polymers and co-polymers containing polyethylene, polypropylene, polystyrene, polyvinyl chloride, synthetic rubber, phenol formaldehyde resin (or Bakelite), neoprene, nylon, polyacrylonitrile, PVB, silicone, polyisobutylene, PEEK, PMMA, and PTFE.

In some embodiments, the pores are filled partially with a thin composite polymer layer to produce a surface modification material that has porosity and functionality provided by the polymer. In other embodiments, the pores are filled completely with a thick polymer layer to produce a surface modification material with a thick polymer layer that has composite properties of the porous base material and the polymer layer. A polymer as described in the compositions herein includes co-polymers.

In some embodiments, a layer of material is deposited that adds one or more functional group(s) to the surface modification material, such as, but not limited to, ammonium groups (e.g., quaternary ammonium groups), alkyl groups, perfluoroalkyl groups, fluoroalkyl groups. In some embodiments, a polymer or ceramic layer is deposited. Examples of functional group(s) and functions thereby imparted include quaternary ammonium groups for anti-microbial functions, alkyl chains for water repellency and hydrocarbon affinity, perfluoroalkyl groups for water and oil repellant functions, polymers for mechanical property function, other ceramics for aesthetic functions, optoelectronic functions, or anti-corrosive functions.

In some embodiments, the pores are substantially or completely filled with a polymer or with a ceramic material.

In some embodiments, a material in the pores interacts with the ceramic material. Examples of such materials and functions thereby imparted include the oxidation of the surface modification material by ambient liquid or vapor, the condensation of minor components (e.g., environmental pollutants), the capture or oxidation of hazardous environmental materials such as CO or H₂S from environmental air, and/or the collection and retention of materials in the environment.

In some embodiments, moisture in the environment or added to the pores interacts with a material in the pores to modify the material in the pores or the surface modification material. Examples of such materials and functions thereby imparted include changes in wetting behavior, in optical properties, changes in oxidation state or reactivity, changes in the rate of evaporation, frosting, icing, or condensation.

In some embodiments, material in the pores may be designed to interact with the ceramic material to “tune” the properties of the overall surface. Examples of tunable properties includes, but are not limited to, wettability, hardness, microbial resistance, catalytic activity, corrosion resistance, acoustic properties, light reflectivity, color, and/or photochemical activity.

In some embodiments, the ceramic surface modification material and a material in the pores interact in a synergistic manner, for example, enhancing or reducing at least one functionality of the surface modification material and/or the material in the pores, in comparison to the functionality of the surface modification material and/or the material in the pores alone. In some embodiments, two or more materials in the pores interact in a synergistic manner, for example, enhancing or reducing at least one functionality of at least one material in the pores, in comparison to the functionality of that material alone.

In some embodiments, the ceramic surface modification material is asymmetric, for example, a pore morphology that is not spherical, cylindrical, cubic or otherwise ordered as having a well-defined, relatively constant, normal distribution of surface area to volume, as characterized a by a ratio of the pore diameter at the first quartile to the pore size at the third quartile as a function of the thickness of the binderless ceramic surface modification. In particular, the pore morphology is asymmetric about its center when compared to a spherical, cylindrical, or cubic structure. A nonlimiting example of asymmetric pores is depicted in PCT Application No. PCT/US19/39743, which is incorporated by reference herein in its entirety.

A porous ceramic material (interconnected ceramic network) may be characterized by a broad pore size distribution that varies with distance from the substrate. In particular, the pore structure at a given distance from the substrate can be characterized locally, e.g., as described herein and has a different characterization at a different distance. The resulting asymmetry is determined in situ by the combination of substrate, ionic mobility, processing conditions such as temperature, pressure, and concentrations. The degree of asymmetry can be further modified through bulk means such as mixing, agitation, electric field modulation, and tank filtration, or through surface directed process means such as shear rates, impinging flows or surface charge modification and modulation. The asymmetry can be determined ex situ through a variety of means such as etching, track etching, ion beam milling, oxidation, photocatalysis, or through additional means. These approaches are to refer to materials which have a narrower, or symmetric pore structures, with thickness and/or pore depth, such as zeolites, track etched membranes, or expanded PTFE membranes.

In some embodiments, the interconnected ceramic network material includes mesoporous mean pore sizes that range from about 2 nm to about 50 nm. In other embodiments, the mean pore sizes range from about 50 nm to about 1000 nm. In some embodiments, the binderless porous ceramic material includes a mean pore diameter of about 2 nm to about 20 nm. In some embodiments, the mean pore diameter is any of at least about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm. In some embodiments, the mean pore diameter is any of about 2 to about 5, about 4 to about 9, about 5 to about 10, about 7 to about 12, about 9 to about 15, about 12 to about 18, about 15 to about 20, about 4 to about 11, about 5 to about 9, about 4 to about 8, or about 7 to about 11 nm.

The interconnected ceramic network material may include one or more metal oxide and/or metal hydroxide (and/or hydrates thereof). Non-limiting examples of metals that may be included in the ceramic compositions disclosed herein include: zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt. In some embodiments, the ceramic material includes a transition metal, a Group II element, a rare-earth element (e.g., lanthanum, cerium gadolinium, praseodymium, scandium, yttrium, samarium, or neodymium), aluminum, tin, or lead. In some embodiments, the ceramic material includes two or more metal oxides (e.g., a mixed metal oxide) including but not limited to zinc, aluminum, manganese, magnesium, cerium, praseodymium, and cobalt.

In some embodiments, the interconnected ceramic network material includes: a mixture of zinc and aluminum oxides and/or hydroxides; a mixture of ZnO and Al₂O₃, and Zn-aluminates; mixtures of materials comprising any/all phases comprising Zn, Al, and oxygen; a mixture of manganese and magnesium oxides and/or hydroxides; manganese oxide; aluminum oxide; a mixed metal manganese oxide and/or hydroxide; a mixture of magnesium and aluminum oxides and/or hydroxides; a mixture of magnesium, cerium, and aluminum oxides and/or hydroxides; a mixture of zinc, gadolinium, and aluminum oxides and/or hydroxides; a mixture of cobalt and aluminum oxides and/or hydroxides; a mixture of manganese and aluminum oxides and/or hydroxides; a mixture of cerium and aluminum oxides and/or hydroxides; a mixture of iron and aluminum oxides and/or hydroxides; a mixture of tungsten and aluminum oxides and/or hydroxides; a mixture of tin and aluminum oxides; tungsten oxide and/or hydroxide; magnesium oxide and/or hydroxide; manganese oxide and/or hydroxide; tin oxide and/or hydroxide; or zinc oxide and/or hydroxide.

In some embodiments, at least one metal in the ceramic material is in the 2⁺ oxidation state.

In some embodiments, the interconnected ceramic network material includes one or more oxide and/or hydroxide of zinc, aluminum, manganese, magnesium, cerium, gadolinium, and cobalt, and the substrate is aluminum or an aluminum alloy.

In some embodiments, the interconnected ceramic network material is superhydrophobic. In some embodiments, the surface modification material is highly hydrophobic. In some embodiments, the surface modification material includes one or more functional characteristic selected from wettability, hardness, elasticity, mechanical, electrical, piezoelectric, electromagnetic, optical, adhesion, or thermal properties, microbial affinity or resistance, alteration of biofilm growth, catalytic activity, permeability, aesthetic appearance, and corrosion resistance, in comparison to a substrate that does not include the ceramic material.

In some embodiments, a functional material layer (e.g., top layer of material) is deposited onto the ceramic material. Examples of such materials include, but are not limited to, quaternary ammonium groups for anti-microbial functions, alkyl chains for water repellency and hydrocarbon affinity, perfluoroalkyl groups for water and oil repellant functions, polymers for mechanical property function, other ceramics for aesthetic functions, optoelectronic functions, or anti-corrosive functions. Examples of functionalities imparted by such materials include, but are not limited to, changes in the porosity, wicking, repellency, and/or wetting behavior; changes in the composite (including the porous material and second material) to modify electrical/dielectric properties, to modify mechanical properties such as abrasion resistance, hardness, toughness, tactile feel, elastic modulus, yield strength, yield stress, Young's modulus, surface (compressive or tensile) stress, tensile strength, compression strength, and/or elasticity; thermal properties such as thermal diffusivity, conductivity, thermal expansion coefficient, thermal interface stress, thermal anisotropy, to modify optical properties such as emissivity, color, reflectivity, and/or absorption coefficients, to modify of chemical properties such as corrosion, catalysis, reactivity, inertness, compatibility, fouling resistance, ion pump blocking, microbial resistance and/or microbial compatibility, promotion of adhesion of subsequent material layers, and/or as a substrate for biocatalysis.

In some embodiments, the interconnected ceramic network material is resistant to degradation by ultraviolet radiation, in comparison to the substrate material, such as a polymer or any of the substrate materials disclosed herein.

In some embodiments, the interconnected ceramic network material includes a thickness of about 0.5 micrometers to about 20 micrometers. In some embodiments, the ceramic material includes a thickness of about 0.2 micrometers to about 25 micrometers. In some embodiments, the thickness is any of at least about 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 micrometers. In some embodiments, the thickness is any of about 0.2 to about 0.5, about 0.5 to about 1, about 1 to about 5, about 3 to about 7, about 5 to about 10, about 7 to about 15, about 10 to about 15, about 12 to about 18, about 15 to about 20, about 18 to about 25, about 0.5 to about 15, about 2 to about 10, about 1 to about 10, about 3 to about 13, about 0.5 to about 15, about 0.5 to about 5, about 0.5 to about 10, or about 5 to about 15 micrometers.

In some embodiments, the interconnected ceramic network material is characterized by a water contact angle of about 0° to about 180°. In other embodiments, the water contact angle is less than about 30 degrees. In other embodiments the water contact angle is greater than about 150 degrees.

In some embodiments, the interconnected ceramic network material includes a surface area of about 1.1 m² to about 100 m² per square meter of projected substrate area. In some embodiments, the ceramic material includes a surface area of about 10 m² to about 1500 m² per square meter of projected substrate area. In some embodiments, the surface area is any of at least about 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m² per square meter of projected substrate area. In some embodiments, the surface area is any of about 10 to about 100, about 50 to about 250, about 150 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 1200, about 1000 to about 1500, about 70 to about 1000, about 150 to about 800, about 500 to about 900, or about 500 to about 1000 m² per square meter of projected substrate area.

In some embodiments, the interconnected ceramic network material includes a surface area of about 15 m² to about 1500 m² per gram of ceramic material. In some embodiments, the surface area is any of at least about 15, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m² per gram of ceramic material. In some embodiments, the surface area is any of about 15 to about 100, about 50 to about 250, about 150 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 1200, about 1000 to about 1500, about 50 to about 700, about 75 to about 600, about 150 to about 650, or about 250 to about 700 m² per gram of ceramic material.

Substrates

The substrate on which a porous ceramic material (interconnected ceramic network) as described herein is applied or deposited may be composed of any material suitable for the structural or functional characteristics, or functional application of use, for example, in a device, such as a heat exchanger. In some embodiments, the substrate is aluminum or contains aluminum (e.g., an aluminum alloy), a ferrous alloy, zinc, a zinc alloy, copper, a copper alloy, a nickel alloy, nickel, a titanium alloy, titanium, a cobalt-chromium containing alloy, glass, a polymer, a co-polymer, a natural material (e.g., a natural material containing cellulose), or a plastic.

In some embodiments, the substrate includes a metal, and the primary metal in an interconnected ceramic network material as described herein is different than the primary metal in the substrate. A primary metal is a metal that is at least about 50%, 60%, 70%, 80%, 90%, or 95% of the total metal in the substrate or the ceramic material, e.g., as determined by x-ray diffraction on an atomic metals basis. Examples of substrate primary metals include, but are not limited to, aluminum, iron, copper, zinc, nickel, titanium, and magnesium. Examples of ceramic primary metals include, but are not limited to, zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt.

In some embodiments, the substrate includes a metal that is able to react (e.g., dissolve) under reaction conditions that allow for local dissolution of the substrate metal, and the substrate metal is incorporated into a substrate modification material, such as a ceramic material, e.g., a binderless porous ceramic material. For example, an aluminum substrate may provide aluminum (e.g., Al³⁺) that is incorporated into ceramic material as the ceramic material is deposited on the substrate.

The following examples are intended to illustrate, but not limit, the invention.

EXAMPLES

Surface modification materials as described in the examples below were prepared as follows. The parts, substrates, or assemblies were cleaned with isopropyl alcohol (IPA) and a towel to remove any residual oils. Polymeric substrates or substrates with pH sensitivity were typically only cleaned with IPA and did not go through the following caustic and acid processing steps. Next, the metallic parts or substrates were submerged in a caustic etch bath at pH>11 at a temperature of about 20° C. to about 60° C. for about 5 minutes to about 20 minutes. The assemblies were then rinsed in water to remove any residual caustic or loosely adhered material. Next, the parts were submerged in a nitric acid solution with pH below 1 and temperature of about 20° C. to about 40° C. to remove the smut and/or deoxidize the substrate. The assemblies were then placed into the production bath containing 20-250 mM of metal nitrate or sulfates or mixed metal nitrates or sulfates and a similar molar amount of a diamine, triamine, or tetramine that were allowed to react and settle at a reaction temperature of 50-85° C. The parts, substrates, or assemblies were maintained in the bath for time periods ranging from about 5 minutes to about 3 hours. The substrates were removed and drained and placed into an oven to dry and/or calcine at a temperature sufficient to convert the ceramic material to a high degree of oxides, such as, but not limited to, about 65% or greater (e.g., to change the ratio of hydroxides/oxides, while preserving some hydroxide), for example, about 50° C.-about 600° C. thermal processing for several minutes to several hours. This deposit step can optionally be repeated before or after the drying step followed by another optional drying step, if desired. After cooling, the parts were further processed and/or tested as described in the examples below.

Example 1

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides. The interconnected porous ceramic surface was deposited in a 25 to 100 mM aqueous solution of magnesium nitrate and a similar amount of hexamethylenetetramine at a temperature of about 50° C. to 80° C. for a time period of about 15 to 90 minutes. The coil was then calcined at a temperature of about 300° C. to about 500° C. for about 1 hour. A scanning electron microscopy (SEM) cross section of the sample was prepared by first covering the top of the ceramic surface with an epoxy resin and then directing a focused ion beam on the top of the sample until sufficient material is removed to expose the side of the interconnected porous ceramic layer. The thickness of the interconnected porous ceramic layer was measured in the direction normal the aluminum substrate surface and found to be about 5 microns. The sample was analyzed using mercury porosimetry, X-ray diffraction (XRD), differential scanning calorimetry, nanoindentation, and polarization resistance. The mercury porosimetry showed that the sample had a pore volume of 1400 mm³/g and a total porosity of 84%. The XRD spectrum in FIG. 1 shows clear peaks at 35.6°, 43.4°, and 62.7°, indicating a crystalline MgO deposit structure.

Example 2

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides in a procedure similar to the procedure described in Example 1. A solution of polystyrene in toluene was cast onto the deposit surface which was held between 20° C. and 35° C. The solvent evaporated until the sample was completely dry.

Example 3

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides in a procedure similar to the procedure described in Example 1. The plate was then immersed into a solution of polystyrene in toluene held between 20° C. and 35° C. After several hours the sample was removed from the solution and the solvent retained on the surface evaporates until the sample was completely dry.

Example 4

A clean 3003 aluminum plate is coated with an interconnected porous ceramic surface based on zinc oxides. Separately, a clean 3003 aluminum plate is coated with an interconnected porous ceramic surface composed of approximately 66% zinc oxide by mass and 34% magnesium oxide by mass. Separately, a clean 3003 aluminum plate is coated with an interconnected porous ceramic surface based magnesium oxide. All three samples are immersed in a solution of polychloroprene in tert-butyl acetate for 90 minutes. The samples are then removed from the solution and cured at 160° C. for 40 minutes under a nitrogen atmosphere.

Each sample is analyzed using a solvent swelling technique with toluene and Fourier-transform infrared spectroscopy (FTIR) to determine the degree of cross linking of the polychloroprene. The sample based on only zinc oxides has the highest degree of cross linking, the sample based on only magnesium oxides has the lowest degree of cross linking, and the sample composed of both zinc oxide and magnesium oxide has a degree of cross linking between the values of the other two samples.

Example 5

A clean 3003 aluminum plate was coated with an porous interconnected ceramic surface modification based on a mixture of zinc and aluminum oxides. The porous ceramic surface modification was deposited in a 25 to 100 mM aqueous solution of zinc nitrate and a similar amount of hexamethylenetetramine at a temperature of about 50° C. to 80° C. for a time period of about 15 to 120 minutes. The coil was then calcined at a temperature of about 350° C. to 550° C. for about 1 hour. The sample was then held at 100° C. and a melt of paraffin wax was drop cast and allowed to wick into the surface. The sample was then allowed to cool to room temperature. 24 hours after cooling to room temperature the sample underwent electrochemical testing. Polarization resistance was conducted on the sample and the corrosion resistance was found to be 2.3×10⁶ ohms. The sample was then subjected to 3 hours of immersion in a corrosive environment following the protocol of ASTM G85-A3, 115 hours of UV exposure following the protocol of ASTM D4587, and 180 hours of water immersion following the protocol of ASTM D870. The sample again underwent polarization resistance testing and the corrosion resistance was found to be 4.2×10⁵ ohms. In comparison polarization resistance was conducted on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides with no paraffin layer and the corrosion resistance was found to be 4.3×10⁴ ohms.

Example 6

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides in a procedure similar to the procedure described in Example 1. The sample was then held at 100° C. and a melt of paraffin wax was drop cast and allowed to wick into the surface. The sample was then allowed to cool to room temperature. 24 hours after cooling to room temperature the sample underwent electrochemical testing. Polarization resistance was conducted on the sample and the corrosion resistance was found to be 1.3×10⁶ ohms. The sample was then subjected to 3 hours of immersion in a corrosive environment following the protocol of ASTM G85-A3, 115 hours of UV exposure following the protocol of ASTM D4587, and 159 hours of water immersion following the protocol of ASTM D870. The sample again underwent polarization resistance testing and the corrosion resistance was found to be 1.7×10⁵ ohms. In comparison polarization resistance was conducted on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides with no paraffin layer and the corrosion resistance was found to be 2.2×10⁴ ohms.

Example 7

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides in a procedure similar to the procedure described in Example 1, but using manganese nitrate or sulfate instead of magnesium nitrate. The sample was then held at 100° C. and a melt of paraffin wax was drop cast and allowed to wick into the surface. The sample was then allowed to cool to room temperature. 24 hours after cooling to room temperature the sample underwent electrochemical testing. Polarization resistance was conducted on the sample and the corrosion resistance was found to be 3.7×10⁶ ohms. The sample was then subjected to 3 hours of immersion in a corrosive environment following the protocol of ASTM G85-A3, 115 hours of UV exposure following the protocol of ASTM D4587, and 159 hours of water immersion following the protocol of ASTM D870. The sample again underwent polarization resistance testing and the corrosion resistance was found to be 1.1×10⁶ ohms. In comparison polarization resistance was conducted on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides with no paraffin layer and the corrosion resistance was found to be 4.6×10⁴ ohms.

Example 8

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides in a procedure similar to the procedure described in Example 7. The sample was then coated with a layer of tung oil by drop casting with a solution of 50% (by volume) tung oil and 50% limonene. After the solution had wicked throughout the entire sample, the sample was hung to dry at room temperature for 3 days.

After drying, polarization resistance was conducted on the sample and the corrosion resistance was found to be 3.4×10⁵ ohms. The sample was then subjected to 3 hours of immersion in a corrosive environment following the protocol of ASTM G85-A3, 115 hours of UV exposure following the protocol of ASTM D4587, and 158 hours of water immersion following the protocol of ASTM D870. The sample again underwent polarization resistance testing and the corrosion resistance was found to be 7.6×10⁵ ohms. In comparison polarization resistance was conducted on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides with no tung oil layer and the corrosion resistance was found to be 4.6×10⁴ ohms.

Example 9

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides in a procedure similar to the procedure described in Example 5. The sample was then coated with a layer of tung oil by drop casting with a solution of 50% (by volume) tung oil and 50% limonene. After the solution had wicked throughout the entire sample, the sample was hung to dry at room temperature for 3 days.

After drying, polarization resistance was conducted on the sample and the corrosion resistance was found to be 8.0×10⁵ ohms. In comparison polarization resistance was conducted on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides with no tung oil layer and the corrosion resistance was found to be 4.3×10⁴ ohms.

Example 10

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides, in a procedure similar to the procedure described in Example 1. The sample was then coated with a layer of tung oil by drop casting with a solution of 50% (by volume) tung oil and 50% limonene. After the solution had wicked throughout the entire sample, the sample was hung to dry at room temperature for 3 days.

After drying, polarization resistance was conducted on the sample and the corrosion resistance was found to be 6.1×10⁵ ohms. In comparison polarization resistance was conducted on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides with no tung oil layer and the corrosion resistance was found to be 2.2×10⁴ ohms.

Example 11

Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides in a procedure similar to the procedure described in Example 5. A interconnected porous ceramic-coated aluminum plate and an additional bare uncoated 3003 aluminum plate were dipped in an 1 to 5% room-temperature vulcanizing (RTV) fluorosilicone solution dispersed in tert-Butyl acetate and retrieved to form a continuous film. The solvent was evaporated until both the samples were completely dry. The plates were moisture-cured for 48 hours at room temperature in an ambient environment. Contact angle measurements were taken on all three plates namely: a) An interconnected porous ceramic surface, b) an interconnected porous ceramic surface partially filled with an RTV silicone, and c) 3003 aluminum plate top coated with RTV silicone. FIG. 1 shows SEM images of all three panels with the highest contact angle of 151° on panel (b) where the interconnected ceramic porous structure is partially filled with RTV silicone. The observed contact angle on panel (c) and (b) was 114° and <15°, respectively. Panel (b) was again dipped in the RTV Silicone solution dispersed in tert-Butyl acetate to completely fill up the interconnected porous ceramic structure and the measured contact angle was 117°. The results are shown in FIGS. 2A-2C.

Example 12

Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides, in a procedure similar to the procedure described in Example 7. An interconnected porous ceramic-coated aluminum plate and an additional bare uncoated 3003 aluminum plate were dipped in a 1-5% polydimethyl siloxane (PDMS) (Sylgard 182) solution dispersed in toluene and retrieved to form a continuous film. The solvent was evaporated until both the samples were completely dry, and plates were cured for 2 hours at 80° C. Contact angle measurements were taken on all three plates namely: a) interconnected porous ceramic surface, b) interconnected porous ceramic surface top coated with a PDMS and c) 3003 aluminum plate top coated with PDMS. FIGS. 3A-3C show SEM images of all three panels with the highest contact angle of 141° on panel (b) where the interconnected ceramic porous structure was partially filled with the topcoat. The observed contact angle on panels (c) and (b) were 117° and <15°, respectively.

Example 13

Three clean 3003 aluminum plates were coated with three sealants based on a) polyurethane (Varathane), b) polyether-based silane-terminated polymer (Geniosil WP1), and c) solvent-based acrylic (Krylon crystal clear acrylic). Polarization resistance was conducted in a 3.5% NaCl solution from −0.15 mV to 0.15 mV versus the open circuit potential on all three plates. The corrosion resistance was measured to be 5.9×10⁷ ohms, 3.7×10² ohms, and 9.7×10³ ohms for polyurethane, polyether-based silane-terminated, and acrylic based surface treatment, respectively. In comparison, polarization resistance was conducted on an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides with no top coat, prepared using a procedure similar to the procedure described in Example 6, and was found to be 1.1×10³ ohms. In comparison, three clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides. The three plates were again with the same polymers as above namely, a) polyurethane b) polyether-based silane-terminated polymer, and c) solvent-based acrylic. The corrosion resistance was measured to be 1.4×10⁸ ohms, 1.4×10⁷ ohms, and 1.0×10⁷ ohms, respectively.

Example 14

Three clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides, prepared using a procedure similar to the procedure described in Example 7, and further filled with different sealants based on a) polyurethane (Varathane ultimate spar) b) water-based polyacrylic (Minwax Polyacrylic) and c) polyether-based silane-terminated polymer (Geniosil WP1). The corrosion resistance was measured and found to be 9.8×10⁷ ohms, 5.7×10⁷ ohms, and 6.5×10⁵ ohms. In comparison, polarization resistance was conducted on a water based polyacrylic sealant coated on a clean 3003 aluminum plate and found to be 9.6×10³ ohms. The corrosion resistance on the interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides on a clean 3003 aluminum plate was 1.7×10⁴ ohms. The sealant resistances on a bare aluminum panel are listed in Example 13.

Example 15

Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides, prepared using a procedure similar to the procedure described in Example 1. One of the plates was dip coated with the water-based Minwax polyacrylic surface treatment and kept at room temperature to allow the surface treatment to wick into the surface. Polarization resistance was conducted on the plate and the corrosion resistance was found to be 2.1×10⁵ ohms. In comparison, the corrosion resistance of the water based polyacrylic sealant coated on a clean 3003 aluminum plate with the same procedure was found to be 1.1×10⁴ ohms.

Example 16

Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides, prepared using a procedure similar to the procedure described in Example 5. One of the samples was sprayed with the aerosol-based polyurethane sealant (Varathane), allowed to wick into the surface, and cured at room temperature for 48 hours. Another clean 3003 aluminum plate was coated with the aerosol-based polyurethane surface treatment with a similar procedure. All three samples were then subjected to 100 hours of salt spray in a corrosive environment following the protocol of ASTM G85-A3 and imaged after cleaning with deionized (DI) water gently, ultrasonicating for 10 min in DI water and drying at room temperature for an hour. FIGS. 4A-4C shows the extent of the corrosion on all the three samples: a) panel modified with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides only, b) a clean 3003 aluminum plate coated with aerosol based polyurethane top coat, and c) panel coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides and filled with aerosol-based polyurethane surface treatment. The composite material (c) prevented the corrosion around the edges, unlike sample (b). Pit densities are listed in FIGS. 4A-4C.

Example 17

Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides, prepared using a procedure similar to the procedure described in Example 1. One of the samples was dipped in water-based polyacrylic sealant (Minwax polyacrylic), allowed to wick into the surface, and cured at room temperature for 24 hours. Another clean 3003 aluminum plate was coated with the water-based polyacrylic sealant as a control. All three samples were then subjected to crosshatch adhesion testing following the protocol of ASTM D3359. FIGS. 5A-5C show the extent of the delamination of the respective coatings on all the three samples a) panel coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides (ASTM Class: 5B), b) 3003 aluminum plate coated with water-based polyacrylic sealant (ASTM Class: 1B) and c) panel coated with an interconnected porous ceramic surface based on a mixture of magnesium and aluminum oxides and filled with water based polyacrylic sealant (5B). The ceramic improved the adhesion performance of the polymer.

Example 18

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides, prepared using a procedure similar to the procedure described in Example 5. Subsequently, the sample was sprayed with acrylic based sealant and dried at room temperature for 24 hours. The sample was then subjected to pencil harness testing following the protocol of ASTM D3363 method and scratch and gouge hardness was found to be HB and 4H, respectively. In comparison, scratch, and gouge hardness of a clean 3003 aluminum plate sprayed, dried with acrylic based top coat following the aforementioned procedure was 5B and 3B respectively.

Example 19

A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides, prepared using a procedure similar to the procedure described in Example 5. Subsequently, the sample was coated with acrylic based sealant with a clean 3003 aluminum plate and both of the samples were visually inspected for any coating defects. As shown in FIGS. 6A-6B, sagging was observed on a clean 3003 aluminum plate coated with acrylic based sealant (FIG. 6A) whereas there was no defect on the panel coated with an interconnected porous ceramic surface and then filled with the acrylic based sealant (FIG. 6B). Sagging was observed on a clean 3003 aluminum plate coated with acrylic based sealant whereas there was no defect on the panel coated with the interconnected porous ceramic surface and then filled with the acrylic based sealant.

Example 20

Epoxy-based resin was dropped on the surface of a clean 3003 aluminum plate and contact angle progression was measured with time (Sample A). In comparison, a clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of zinc and aluminum oxides, prepared using a procedure similar to the procedure described in Example 5, and measured for contact angle progression with time (Sample B). Another clean 3003 aluminum plate was coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides, prepared using a procedure similar to the procedure described in Example 7, and checked for self-leveling properties following the same aforementioned protocol, by measuring the contact angle progression with time against an epoxy-based resin (Sample C). FIGS. 7A-7C show the self-leveling phenomenon comparison of all the three plates.

Example 21

Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of zinc/aluminum oxides and manganese/aluminum oxides (prepared using procedures similar to the procedures described in Examples 5 and 7, respectively). Contact angle measurements using a drop of a water based polyacrylic surface treatment were taken on both the plates and found to be approximately 57° and <15°, respectively. To showcase self-levelling phenomenon in comparison, the contact angle of a water based polyacrylic surface treatment on a clean 3003 aluminum plate was 73° as shown in FIG. 8 .

Example 22

Two clean 3003 aluminum plates (2×4 in²) were coated with an interconnected porous ceramic surface based on a mixture of zinc/aluminum oxides and manganese/aluminum oxides (prepared using procedures similar to the procedures described in Examples 5 and 7, respectively). 180 mg of paraffin wax with a melting point less than 70° C. was dropped in the middle of each sample kept on a hot plate at 100° C. to check for wicking behavior. In comparison, 180 mg of paraffin wax was also dropped in the middle of a clean 3003 Al plate also kept on a hot plate at 100° C. FIG. 9 showcases the comparison of all the samples and the converge of the paraffin achieved on the sample after 5 min. Paraffin area % coverage on each sample was determined using the region of interest function of ImageJ and measured to be 93.1% for zinc/aluminum based surface, 66.4% for manganese/aluminum based surface, and 23.5% for 3003 Aluminum plate. FIG. 10 showcases the wicking behavior of paraffin wax on all the three substrates. In the zinc/aluminum based ceramic surface, paraffin was also able to wick through the edges to the back side of the panel. The penetration of the paraffin from the edges was measured on the back of the panel and was approximately 2 mm towards the middle of the sample on the back side.

Example 23

A brazed aluminum heat exchanger with a thickness of about 3 centimeters was coated with a binderless structured ceramic material based on manganese and aluminum oxides, prepared using a procedure similar to the procedure described in Example 7. The sample was heated in a dry oven, then sprayed with hot paraffin wax on both sides. The wax was wicked inward by the structured ceramic layer creating a more uniformly coated component than a heat exchanger without the structured ceramic material.

Example 24

Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface based on a mixture of manganese and aluminum oxides, prepared using a procedure similar to the procedure described in Example 7. 200 μL of 2 wt % polysilazane (Durazane 1500) solution dispersed in n-Butyl acetate was drop casted on an interconnected porous ceramic-coated aluminum plate (Panel A) and on an additional bare uncoated 3003 aluminum plate (Panel B). Following a similar procedure, 200 μL of 20 wt % polysilazane solution was drop casted on another interconnected porous ceramic-coated aluminum plate (Panel C) and an additional bare uncoated 3003 aluminum plate (Panel D). The solvent was evaporated until all four samples were completely dry and cured at 200° C. for 8 hours. Contact angle measurements were taken on all panels using a 2 μL droplet of DI water. The measured contact angles were 141°, 97°, 150°, and 81° for Panel A, Panel B, Panel C, and Panel D, respectively. The samples were then subjected to pencil hardness testing following the protocol of ASTM D3363 method and scratch and gouge hardness was measured and found to be 4B & 3H for Panel A, 2B & 2H for Panel B, 4B and 4H for Panel C and 2B and 5H for Panel D, respectively.

Example 25

Following a procedure similar to the procedure described in Example 24, two interconnected porous ceramic-coated aluminum plates were coated and cured with 2 wt. % (Panel E) & 20 wt. % (Panel G) Durazane 1800 based formulation. Additional two bare uncoated 3003 aluminum plates were coated and cured with 2 wt. % (Panel F) & 20 wt. % (Panel H) Durazane 1800 based formulation. Contact angle measurements were taken on all the panels using a 2 μL droplet of DI water. The measured contact angles were 141°, 87°, 108°, and 75° for Panel E, Panel F, Panel G, and Panel H, respectively. The samples were then subjected to pencil hardness testing following the protocol of ASTM D3363 method and scratch and gouge hardness was measured and found to be HB & 3H for Panel E, H & 4H for Panel F, 2H and 5H for Panel G and 3HB and 6H for Panel H, respectively.

Example 26

A thin film of cellulose acetate was coated with an interconnected porous ceramic coating based on zinc oxide. The film was oxidized using a dilute aqueous solution of potassium persulfate. The film was then coated with a zinc oxide-based interconnected porous ceramic surface modification using methods similar to methods described in the examples above. The electrical resistance, as measured by a linear 4-point probe measurement, of the cellulose acetate bare film was out of the range of the instrument (greater than 10{circumflex over ( )}10 ohms). The zinc oxide coated cellulose acetate film was measured to have an electrical resistance of about 10{circumflex over ( )}6 to about 10{circumflex over ( )}7 ohms. The electrical resistance of the film was reduced upon coating it with the interconnected porous zinc oxide ceramic layer.

Although the foregoing invention has been described in some detail by way of illustration and examples for purposes of clarity of understanding, it will be apparent to those skilled in the art that certain changes and modifications may be practiced without departing from the spirit and scope of the invention. Therefore, the description should not be construed as limiting the scope of the invention.

All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entireties for all purposes and to the same extent as if each individual publication, patent, or patent application were specifically and individually indicated to be so incorporated by reference. 

1. A composition comprising: (i) a composite material, said composite material comprising: a polymer, wax, and/or resin impregnated into a porous ceramic material, wherein the porous ceramic material comprises an interconnected network of ceramic and an accessible pore volume that is at least partially filled with said polymer, wax, and/or resin; and (ii) a substrate, wherein the composite material is in contact with the substrate.
 2. The composition according to claim 1, wherein the substrate and the ceramic material each comprise a primary metal, and wherein the primary metal in the ceramic material is different than the primary metal in the substrate.
 3. The composition according to claim 1, wherein the composite material comprises a thickness of about 1 micrometer to about 100 micrometers.
 4. The composition according to claim 1, wherein at least about 20% of the total ceramic content by mass in the composite material is interconnected.
 5. (canceled)
 6. The composition according to claim 1, wherein the composite material comprises a plurality of interconnected networks of ceramic material.
 7. (canceled)
 8. The composition according to claim 1, wherein the ceramic material comprises a rare earth element, a transition metal element, an alkaline earth metal, element or aluminum.
 9. The composition according to claim 1, wherein the ceramic material comprises an oxide, a hydroxide, and/or a layered double hydroxide.
 10. (canceled)
 11. A composition according to claim 1, wherein the substrate comprises an aluminum alloy, a steel alloy, a nickel alloy, a titanium alloy, a polymer, a cellulosic material, a polysaccharide, wood, cotton, or glass.
 12. The composition according to claim 1, wherein the polymer, wax, and/or resin imparts one or more functional characteristic selected from: enhanced hardness, elasticity, viscoelasticity, adhesion, thermal properties, aesthetic appearance, liquid repellency, and corrosion resistance, in comparison to an identical ceramic material that does not comprise the polymer, resin, and/or wax on an identical substrate
 13. The composition according to claim 1, wherein the ceramic material is a binderless ceramic material.
 14. The composition according to claim 1, wherein the polymer, wax, and/or resin comprises: a polymer derived from tung oil, linseed oil, walnut oil, natural rubber, cellulose, or chitin; a polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyethylene terephthalate, polyacrylate, poly(methyl methacrylate), polyvinyl acetate, polyether, polychloroprene, poly(vinyl chloride), polyurethane, polyamide, polyimide, silicone, poly(dimethyl siloxane), or a polyepoxide polymer; a silane, a silicate, a siliconate, a polysilazane, an organotriethoxysilane, or an organotrimethoxysilane; or a petroleum wax, an animal produced wax, a plant derived wax, or a mineral derived wax. 15.-19. (canceled)
 20. The composition according to claim 1, wherein the polymer, wax, and/or resin comprises one or more additional additive selected from: lubricants, plasticizers, flame retardants, dyes, UV-stabilizers, free radical scavengers, and cross-linking agents
 21. The composition according to claim 20, wherein the additive imparts one or more property to the composite material selected from viscosity, flexibility, flammability, color, UV stability, chemical reactivity, and degree of cross linking.
 22. The composition according to claim 1, wherein greater than about 1% of the accessible pore volume is filled with said polymer, wax, and/or resin, as determined by mercury porosimetry testing.
 23. The composition according to claim 1, wherein the thickness of the polymer, resin, and/or wax is less than about 1.5 times the thickness of the ceramic material.
 24. The composition according to claim 1, wherein the ceramic material interacts with the polymer, wax, and/or resin material, thereby increasing a rate and/or degree of cross-linking of said polymer, wax, and/or resin, in comparison to the rate and/or degree of cross-linking when the polymer, wax and/or resin is applied directly to an identical substrate that does not comprise the ceramic material.
 25. The composition according to claim 1, wherein the ceramic material interacts with the polymer, wax, and/or resin material, thereby increasing a degree of crystallinity of the polymer, wax, and/or resin material, in comparison to degree of crystallinity when the polymer, wax, and/or resin material applied directly to an identical substrate that does not comprise the ceramic material.
 26. The composition according to claim 1, wherein the ceramic material interacts with the polymer, wax, and/or resin material, thereby decreasing a rate of UV degradation of the polymer, wax, and/or resin material, in comparison to rate of UV degradation of the polymer, wax, and/or resin material applied directly to an identical substrate that does not comprise the ceramic material
 27. The composition according to claim 1, wherein the ceramic material comprises magnesium, manganese, a zinc oxide, or an aluminum oxide or hydroxide, and the polymer, wax, and/or resin comprises a drying oil such as tung oil or paraffin.
 28. The composition according to claim 1, wherein the ceramic material comprises magnesium, manganese, a zinc oxide, or an aluminum oxide or hydroxide, and the polymer, wax, and/or resin reacts chemically with the ceramic material to modify the properties of the polymer, wax, and/or resin.
 29. (canceled)
 30. The composition according to claim 1, wherein the composite material is applied to impart one or more functional property to the substrate, selected from: corrosion protection for the substrate; durability modifier for adhesion and/or fouling surfaces; adhesion promoting or retarding configuration; tactile modified surface; liquid repellency application; optical property modification; mechanical modification such as hardness, elasticity and viscoelasticity; surface and scratch self-healing and repair purposes; separations applications; electrical property modification or electrical property applications; ice, condensate and frost mitigation and/or modification; surface uniformity; defect reduction; and aesthetic properties, and wherein the functional property is improved or of greater magnitude in comparison to an identical porous ceramic material without the polymer, resin, and/or wax on an identical substrate, or in comparison to an identical substrate on which the polymer, resin, and/or wax is applied directly.
 31. (canceled) 